Silver halide emulsions containing hydroxy substituted alicyclic compounds

ABSTRACT

Silver halide photographic emulsions containing antifogging, sensitizing hydroxy-substituted alicyclic compounds. The present invention relates to a silver halide photographic emulsions and a process for the preparation thereof. More particularly, the present invention relates to a silver halide photographic emulsion containing a compound which has simultaneous sensitizing and antifogging effects and a process for the preparation thereof. Hitherto, in order to increase the sensitivity of a silver halide photographic emulsion, chemical ripening, e.g., sulfur sensitization, reduction sensitization or gold sensitization has been carried out during the preparation of the emulsion. In addition, various sensitizers have been added to the final photographic emulsion after chemical ripening. However, it is known that fog increases as the sensitivity of the silver halide photographic emulsion is increased. Such fog is a fatal defect in photographic light-sensitive materials. Many attempts have been previously made to remove such fog. Many attempts have been previously made to remove such fog. For instance, an antifoggant or stabilizer has been added to the final silver halide photographic emulsion for reducing fog formation after chemical ripening. However, the fog cannot be completely removed by this method, and other defects sometimes result from the use of additives which have an adverse effect upon photographic properties. An object of this invention, therefore, is to provide sensitized silver halide photographic emulsions having decreased fog and a process for the production thereof. This object is attained by adding an alicyclic compound having two or more hydroxy groups attached either directly to the ring or to a side chain to a silver halide photographic emulsion. Preferred alicyclic compounds for use in the present invention are substituted alicyclic hydrocarbons having four to six carbon atoms in the ring, wherein the substituents are selected from the group consisting of hydrogen, alkyl having one to four carbon atoms, hydroxy and hydroxy-alkyl having one to four carbon atoms, at least two of said substituents being selected from the group consisting of hydroxy and hydroxy-alkyl. Typical alicyclic compounds as described above to be used in the present invention are as follows:   The compounds of this invention act as both sensitizer and antifoggant and provide superior sensitizing effects as compared with sensitizers used hitherto. Further, these compounds have the ability to decrease the fog, which would otherwise increase as the sensitivity increased. Accordingly, the silver halide emulsions of this invention have remarkably low fog formation and excellent sensitivity as compared with known prior art emulsions. The compounds of this invention may be added to the silver halide emulsion after chemical ripening together with other additives in accordance with conventional practice, or they may be added to the silver halide emulsion after conventional physical ripening. Notably excellent results are obtained when the addition takes place at the beginning of chemical ripening. The amount of the compound employed depends upon the result desired, the degree of ripening, kind of emulsion, etc. Amounts of about 2-100 g., and especially 5-50 g. per mol of silver halide present are preferred. No adverse effects on the photographic properties of the film result from the addition of these compounds in combination with other photographic additives usually employed, such as optical sensitizers, coating aids, hardening agents and plasticizers. Further, these compounds may be used in any kind of silver halide photographic emulsion, such as orthochromatic emulsions, panchromatic emulsions, emulsions for X-ray photographic films, emulsions for photographic papers and color photographic films, with any conventional binder such as gelatin and polyvinyl alcohol, and on any kind of support such as glass, cellulose triacetate film, polyethylene terephthalate film and barita paper. The invention will be illustrated by the following examples wherein AgX is total silver halide present.

United States Patent [72] inventors v Nobuo Yamamoto;

Akilrazu Mikawa; Minoru Sonoda, all of Kamagawa, Japan [21 Appl. No.834,880

[22] Filed June 19, 1969 [45] Patented Nov. 9, 1971 [73] Assignee FujiPhoto Film Co., Ltd.

Kanagawa, Japan [32] Priority June 19, 1968 [33] Japan [54] SILVERHALIDE EMULSIONS CONTAINING HYDROXY SUBSTITUTED ALICYCLIC COMPOUNDS 8 12Claims, No Drawings [52] U.S. Cl 96/107, 96/ l 09 [5 1] Int. Cl G03c1/28, G03c 1/34 [50] Field of Search 96/109, 107

[56] References Cited OTHER REFERENCES Chemical Abstracts vol. 59, l963,column 159a.

Primary Examiner-Norman G. Torchin Assistant Examiner-R. FichterAttorney-Sughrue, Rothwell, Mion, Zinn & Macpeak ABSTRACT: Silver halidephotographic emulsions containing antifogging, sensitizinghydroxy-substituted alicyclic compounds.

SILVER HALIDE EMULSIONS CONTAINING HYDROXY SUBSTITUTED ALICYCLICCOMPOUNDS The present invention relates to a silver halide photographicemulsions and a process for the preparation thereof. More particularly,the present invention relates to a silver halide photographic emulsioncontaining a compound which has simultaneous sensitizing and antifoggingeffects and a process for the preparation thereof.

Hitherto, in order to increase the sensitivity of a silver halidephotographic emulsion, chemical ripening, e.g., sulfur sensitization,reduction sensitization or gold sensitization has been carried outduring the preparation of the emulsion. In addition. various sensitizershave been added to the final photographic emulsion after chemicalripening.

However, it is known that fog increases as the sensitivity of the silverhalide photographic emulsion is increased. Such fog is a fatal defect inphotographic light-sensitive materials. Many attempts have beenpreviously made to remove such fog. Many attempts have been previouslymade to remove such fog. For instance, an antifoggant or stabilizer hasbeen added to the final silver halide photographic emulsion for reducingfog formation after chemical ripening.

However, the fog cannot be completely removed by this method, and otherdefects sometimes result from the use of additives which have an adverseeffect upon photographic properties.

An object of this invention, therefore, is to provide sensitized silverhalide photographic emulsions having .decreased fog and a process forthe production thereof. This object is attained by adding an alicycliccompound having two or more hydroxy groups attached either directly tothe ring or to a side chain to a silver halide photographic emulsion.

Preferred alicyclic compounds for use in the present invention aresubstituted alicyclic hydrocarbons having four to six carbon atoms inthe ring, wherein the substituents are selected from the groupconsisting of hydrogen, alkyl having one to four carbon atoms, hydroxyand hydroxy-alkyl having one to four carbon atoms, at least two of saidsubstituents being selected from the group consisting of hydroxy andhydroxy-alkyl.

Typical alicyclic compounds as described above to be used in the presentinvention are as follows:

Compound (1) H,C-CH,

CH-OH 1,2-eyclopentanedlol I;CC

Compound (2) Compound (3) CH-OH l-methy12,3-eyclopentanediol H C-CH 6HCompound (4) Compound (6) C H-C H;

11,0 CH-OH 1,2-cyclohoxanedlol on cu Compound (7) GHQ-CH1 mo cit-0H1,3-cyclohexanediol CHCHg Compound (8) CII CH I ()IIC CH-OH(015-)lA-cyclohexanediol CH C g Compound (9) (Ill -CH,

llO IIC CII-OH (trans-) 1,4 cyololmxunedimethnnnl CH -CH,

Compound (10) CH -CH,

HOOH -HC CH-CHgOH 1,4-cyclohexanedimethanol Compound (11) C x- 2 CH2 CH,C l-rnethyI-l,2-eyclohexandiol CH -CH OH OH Compound (12) GIL-CH,

H,C\ CIICH,OH Z-hydroxymethylcyclohexanol CHrfiJfi Compound (13) g on Eoil-0H, 5 I1 0 CH-OII 1,3,5-cyclohexanetrlol CHC 1 The compounds of thisinvention act as both sensitizer and antifoggant and provide superiorsensitizing effects as compared with sensitizers used hitherto. Further,these compounds have the ability to decrease the fog, which wouldotherwise increase as the sensitivity increased. Accordingly, the silverhalide emulsions of this invention have remarkably low fog formation andexcellent sensitivity as compared with known prior art emulsions.

The compounds of this invention may be added to the silver halideemulsion after chemical ripening together with other additives inaccordance with conventional practice, or they may be added to thesilver halide emulsion after conventional .physical ripening. Notablyexcellent results are obtained when the addition takes place at thebeginning of chemical ripening. The amount of the compound employeddepends upon the result desired, the degree of ripening, kind ofemulsion, etc.

Amounts of about 2-l00 g., and especially 5-50 g. per mol of silverhalide present are preferred.

Noadverse effects on the photographic properties of :the

film result from the addition of these compounds in combina- 7 tion withother photographic additives usually employed, such as opticalsensitizers, coating aids, hardening agents and plasticizers.

Further, these compounds may be used in any kind of silver halidephotographic emulsion, such as orthochromatic emulsions, panchromaticemulsions, emulsions for X-ray photographic films, emulsions forphotographic papers and color photographic films, with any conventionalbinder such as gelatin and polyvinyl alcohol, and on any kind of supportsuch as glass. cellulose triacetate film, polyethylene terephthalatefilm and barita paper.

The invention will be illustrated by the following examples wherein AgXis total silver halide present.

EXAMPLE 1 into a gelatino silver iodobromide emulsion not yet chemicallysensitized (1.5 percent mol percent Agl and 150 g. of gelatine per 1 molAgX 1,2-cyc1opentanediol (Compound 1) 1-methyl-2,3-cyclopentanediol(Compound 3), l,4-cyclohexane dimethanol (Compound orl-methyl-1,2-cyclohexanediol (Compound 1 l was added. Then 2 g. of asensitizing gelatin which contains a natural sulfur sensitizer, 0.3 mg.ofi HAuCl,-4H O as the gold sensitizer and an aqueous solution of 50 mg.of KSCNS per 1 mol of silver were added in the desired; amount. Thesecond ripening was then carried out with stir-i ring at 53 C. for aprescribed period of time. After addingi chrome alum and saponin intothus resulting emulsion, it was; applied to cellulose triacetate filmand dried. The same photo-E graphic film as described above but notincluding any additive of this invention was prepared as a controlsample for comparison. These photographic films were exposed to light bythe NSG 11 type sensitometer and treated with a developing solutionhaving the following composition at C. for 4 minutes.

Composition of the Developing Solution N-methyl-p-aminophenol sulfate4.0 g. Anhydrous sodium sulfite 60.0 g. Hydroquinone 10.0 g. Anhydroussodium carbonate 53.0 g. Potassium bromide 2.5 g. Water to make 1 literResults obtained are shown in the following table. The speed wascalculated from the amount of exposure required to: produce an opticaldensity of 0.3 above fog, and was shown relatively on the basis of 100at 125 minutes of ripening of the control.

Compound Concentration Ripening Ripening Ripening g./mol of AgX I min.140 min. 155 minutes speed fog speed fog speed fog None (control 1000.09 107 0.ll 137 0.141 (1) l7.3 115 0.07 141 0.09 050 0.11 1 (3) 19.7117 0.07 139 0.09 156 0.11 (10) 20.4 121 0.05 149 0.06 165 007 (II) 22.5125 0.06 147 0.07 160 0.08

It is clear from the above table that the speed increases and the fogdecreases in the silver halide photographic emulsions of this inventionas compared with the control emulsion.

EXAMPLE 2 Into a gelatino silver iodobromide emulsion for highsensitivity negative film (7 mol percent Agl and 200 g. ofgelatin per 1mol of AgX), 1,2-cyclohexanediol (Compound 6), 1,3- cyclohexanediol(Compound 7), cis-l,4-cyclohexanediol (Compound 8) ortrans-l,4-cyclohexanediol (Compound 9) was added. Then sulfur and goldsensitizing treatments were carried out at 52 C. Each of the resultingmixtures was applied to a cellulose acetate film so that the coatingamount of silver was mg/100 cm?. The same photographic film as describedabove but not containing an additive of this invention was prepared as acontrol sample for comparison.

These photographic films were exposed to light by the NSG 11 typesensitometer and developed using a developing solution having thefollowing composition at 20 C. for 7 minutes. 5

Composition of the Developing Solution N-methyl-p-aminophenol sulfateAnhydrous sodium sulfite Hydroquinone 5.0 g. Borax 2.0 g. Water torn keI 1 liter The results thus obtained are shown in the following table.The speed was calculated from the amount of exposure required to producean optical density of 0.3 above fog, and

' was shown relatively onthe basis of 100 at minutes ripenanediol,

ing of the control.

Coneon- Ripenlng Riponing Ripening tratlon, 50 min. 65 min. 70 mln.gJmol.

0 AgX Speed Fog Speed Fog Speed Fog N one (control) 0. 10 0.17 131 0. 30Compound 0. l9. 4 103 0. 06 131 0. 07 137 0. 10 Compound 7. 19. 4 105 0.07 131 0. 07 140 0. 11 Compound 8. 19.4 103 0. 06 0. 07 0. 11 19.4 0130.06 129 0. 08 138 0.12

Compound 0.

it is clear from the above table that the speed increases and the fogdecreases in the silver halide photographic emulsions produced by theprocess of this invention.

EXAMPLE 3 A gelatino silver iodobromideemulsion for a high sensitivityradiographic film (1.5 mol percent Agl and g. of gelatin per 1 mol ofAgX) subjected to sulfur and gold sensitizations were prepared. Justbefore application of the emulsion to a support, 2-hydroxymethyl hexanol(Compound 12) or 1,3,5- cyclohexanetriol (Compound 13) was added to theemulsion, and then chrome alum and saponin were added thereto. Theemulsion was then applied to a cellulose triacetate film and dried. Thesame photographic film as described above but not containing an additiveof this invention was produced as a control for comparison. These filmswere exposed to light and developed as in example 1. The results wereshown in the following table, in which the relative speed based on aspeed of 100 for the control was calculated from the exposure requiredto provide an optical density of 0.3 above fog.

Compound Concentration Speed Fog g-lmol of AgX (fog 0.3)

None (control) 100 2.13 0.50

being selected from the group consisting of hydroxy and hydroxy-alkyl.

2. The silver halide photographic emulsion of claim 1 wherein saidsubstituted alicyclic hydrocarbon is a member selected from the groupconsisting of 1,2-cyclopentanediol, 1,2-cyclobutanediol,l-methyl-2,3-cyclopentancdiol, 1,3- cyclopentanediol, Z-hydroxymethylcyclopentanoL. 1,2- cyclohexanediol, 1,3-cyclohexanediol, cis-l,4-cyclohextrans-1,4-cyclohexanediol, 1,4-cyclohexanedimethanol,1-methyl-l,Z-cyclohexanediol, 2-hydroxymethyl-cyclohexanol and1,3,5-cyclohexanetriol.

3. The silver halide photographic .emulsion of claim 1 wherein saidsubstituted alicyclic hydrocarbon is present in the range of from about2 to 100 g. per mole of silver halide.

4. The silver halide photographic emulsion of claim 1 wherein saidsilver halide photographic emulsion is a silver iodobromide emulsion.

5. A process for preparing a silver halide photographic emulsion whichcomprises adding a sensitizing amount of a substituted alicyclichydrocarbon having four to six carbon atoms in the ring, wherein thesubstituents are selected from the group consisting of hydrogen, alkylhaving one to four carbon atoms, hydroxy and hydroxy-alkyl having one tofour carbon atoms, at least two of said substituents being selected fromthe group consisting of hydroxy and hydroxy-alkyl, to a physicallyripened silver halide emulsion prior to chemical ripening.

6. A photographic element comprising a support having coated thereon atleast one silver halide emulsion layer containing a sensitizing amountof a substituted alicyclic hydrocarbon having four to six carbon atomsin the ring, wherein the substituents are selected from the groupconsisting of hydrogen, alkyl having one to four carbon atoms, hydroxyand hydroxy-alkyl having one to four carbon atoms, at least two of saidsubstituents being selected from the group consisting of hydroxy andhydroxy-alkyl.

7. The process of claim 5 wherein said substituted alicyclic hydrocarbonis a member selected from the group consisting of l,2-cyclopentanediol,l,2-cyclobutanediol, l-methyl-2,3- cyclopentanediol,1,3-cyclopentanediol, 2-hydroxymethyl cyclopentanol,l,2-cyclohexanediol, 1,3-cyclohexanediol, cisl,4-cyclohexanediol, transl,4-cyclohexanediol, 1,4- cyclohexanedimethanol,l-methyl-l,2-cyclohexanediol, 2-

hydroxymethyl-cycloehexanol and 1,3,5-cyclohexanetriol.

8. The process of claim 5 wherein said substituted alicyclic hydrocarbonis present in the range of from about 2 to 100 g. per mole of silverhalide.

9. The process of claim 5 wherein said silver halide photographicemulsion is a silver iodobromide emulsion.

10. The photographic element of claim 6 wherein said substitutedalicyclic hydrocarbon is a member selected from the group consisting ofl,2-cyclopentanediol, l,2-cyclobutanediol,l-methyl-2,3-cyclopentanediol, l ,3-cyclopentanediol, 2-hydroxymethylcyclopentanol, l,2-cyclohex-

2. The silver halide photographic emulsion of claim 1 wherein saidsubstituted alicyclic hydrocarbon is a member selected from the groupconsisting of 1,2-cyclopentanediol, 1,2-cyclobutanediol,1-methyl-2,3-cyclopentanediol, 1,3-cyclopentanediol, 2-hydroxymethylcyclopentanol, 1,2-cyclohexanediol, 1,3-cyclohexanediol,cis-1,4-cyclohexanediol, trans-1,4-cyclohexanediol,1,4-cyclohexanedimethanol, 1-methyl-1, 2-cyclohexanedioL,2-hydroxymethyl-cyclohexanol and 1,3,5-cyclohexanetriol.
 3. The silverhalide photographic emulsion of claim 1 wherein said substitutedalicyclic hydrocarbon is present in the range of from about 2 to 100 g.per mole of silver halide.
 4. The silver halide photographic emulsion ofclaim 1 wherein said silver halide photographic emulsion is a silveriodobromide emulsion.
 5. A process for preparing a silver halidephotographic emulsion which comprises adding a sensitizing amount of asubstituted alicyclic hydrocarbon having four to six carbon atoms in thering, wherein the substituents are selected from the group consisting ofhydrogen, alkyl having one to four carbon atoms, hydroxy andhydroxy-alkyl having one to four carbon atoms, at least two of saidsubstituents being selected from the group consisting of hydroxy andhydroxy-alkyl, to a physically ripened silver halide emulsion prior tochemical ripening.
 6. A photographic element comprising a support havingcoated thereon at least one silver halide emulsion layer containing asensitizing amount of a substituted alicyclic hydrocarbon having four tosix carbon atoms in the ring, wherein the substituents are selected fromthe group consisting of hydrogen, alkyl having one to four carbon atoms,hydroxy and hydroxy-alkyl having one to four carbon atoms, at least twoof said substituents being selected from the group consisting of hydroxyand hydroxy-alkyl.
 7. The process of claim 5 wherein said substitutedalicyclic hydrocarbon is a member selected from the group consisting of1, 2-cyclopentanediol, 1,2-cyclobutanediol,1-methyl-2,3-cyclopentanediol, 1,3-cyclopentanediol, 2-hydroxymethylcyclopentanol, 1,2-cyclohexanediol, 1,3-cyclohexanediol,cis-1,4-cyclohexanediol, trans-1,4-cyclohexanediol,1,4-cyclohexanedimethanol, 1-methyl-1,2-cyclohexanediol,2-hydroxymethyl-cyclohexanol and 1,3,5-cyclohexanetriol.
 8. The processof claim 5 wherein said substituted alicyclic hydrocarbon is present inthe range of from about 2 to 100 g. per mole of silver halide.
 9. Theprocess of claim 5 wherein said silver halide photographic emulsion is asilver iodobromide emulsion.
 10. The photographic element of claim 6wherein said substituted alicyclic hydrocarbon is a member selected fromthe group consisting of 1,2-cyclopentanediol, 1,2-cyclobutanediol,1-methyl-2,3-cyclopentanediol, 1,3-cyclopentanediol, 2-hydroxymethylcyclopentanol, 1,2-cyclohexanediol, 1,3-cyclohexanediol,cis-1,4-cyclohexanediol, trans-1,4-cyclohexanediol,1,4-cyclohexanedimethanol, 1-methyl-1,2-cyclohexanediol,2-hydroxymethylcyclohexanol and 1,3,5-cyclohexanetriol.
 11. Thephotographic element of claim 6 wherein said substituted alicyclichydrocarbon is present in the range of from about 2 to 100 g. per moleof silver halide.
 12. The photographic element of claim 6 wherein saidsilver halide photographic emulsion is a silver iodobromide emulsion.